Discontinuous coarsening behavior of Ni(2)MnAl intermetallic compound during isothermal aging treatment of Fe-Mn-Ni-Al alloys.

The discontinuous reaction of the Ni(2)MnAl intermetallic phase was investigated during the aging of a solution-treated Fe-8.3Mn-8.2Ni-4.2Al alloy. During aging, Ni(2)MnAl lamellae formed at the prior austenite grain boundaries and twin boundaries and grew into the neighboring grains. The presence of continuously precipitated fine Ni(2)MnAl particles before the growth of the discontinuously precipitated lamellae was confirmed by dark-field transmission electron microscopy, and it was concluded that the present reaction is a type of discontinuous coarsening process, alpha' + Ni(2)MnAl (continuous precipitation) --> alpha + Ni(2)MnAl (discontinuous coarsening). The chemical driving force and the reduction of the total coherent strain energy were suggested to be the driving force for the discontinuous coarsening reaction.

Quantitative structural analysis of twin boundary in alpha-Zn7Sb2O12 using HAADF STEM method.

The structure and composition of the 1/4{110} twin boundary in alpha-Zn7Sb2O12 have been determined by using quantitative high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) analysis. The noise in the experimental HAADF STEM images is reduced by using the maximum entropy method and average processing, and the parameters used in dynamical simulations are experimentally determined. From the analysis, it has been found that octahedral sites in the twin boundary slightly shift parallel to the [110] direction, and a reduction of the Sb concentration at the octahedral sites on the plane adjacent to the twin boundary was detected. The reduction was measured from three regions in the same twin boundary, and the Sb concentrations were 4 +/- 3, 8 +/- 3 and 19 +/-2 at% from 33 at%.

Development of a stage-scanning system for high-resolution confocal STEM.

A stage-scanning system is composed of a specially designed transmission electron microscopy specimen holder equipped with a piezo-driven specimen stage, power supplier and control software. This system enables the specimen to be scanned three-dimensionally, and therefore confocal scanning transmission electron microscopy (STEM) can be performed with a fixed electron-optics configuration. It is demonstrated that stage-scanning confocal STEM images can be obtained with the lateral atomic resolution and the specimen can be moved three-dimensionally with high precision.

X-ray analysis and mapping by wavelength dispersive X-ray spectroscopy in an electron microscope.

A compact and easy-to-use wavelength dispersive X-ray spectrometer using a multi-capillary X-ray lens attached to a scanning (transmission) electron microscope has been tested for thin-film analysis. B-K spectra from thin-film boron compounds (B4C, h-BN, and B2O3) samples showed prominent peak shifts and detailed structural differences. Mapping images of a thin W/Si double-layer sample resolved each element clearly. Additionally, a thin SiO2 film grown on a Si substrate was imaged with O-K X-rays. Energy and spatial resolution of the system is also discussed.

Development and application of an internet electron microscopy system for the outreach program in Japan.

The development of a remotely operated scanning electron microscopy (SEM) system and its use by high school students and the public as an outreach program are reported. The SEM and the server are located in the National Institute for Materials Science, Tsukuba, Japan, with client computers installed at a science museum and high schools. Using a secure virtual private network system and scheduling/management groupware, observation of SEM images and energy dispersive X-ray analysis are widely and frequently performed throughout Japan.

Sample preparation of GaN-based materials on a sapphire substrate for STEM analysis.

In this work, a detailed TEM sample preparation recipe based on a wedge polishing technique for GaN-based materials is presented. The obtained samples have atomically flat surfaces without any obvious surface damages such as the formation of amorphous layers. A composition estimation of Al(x)Ga(1-x)N from Z-contrast STEM imaging is carried out using these samples. The results are in good accord with the nominal composition.

Nanofabrication by advanced electron microscopy using intense and focused beam∗.

The nanogrowth and nanofabrication of solid substances using an intense and focused electron beam are reviewed in terms of the application of scanning and transmission electron microscopy (SEM, TEM and STEM) to control the size, position and structure of nanomaterials. The first example discussed is the growth of freestanding nanotrees on insulator substrates by TEM. The growth process of the nanotrees was observed in situ and analyzed by high-resolution TEM (HRTEM) and was mainly controlled by the intensity of the electron beam. The second example is position- and size-controlled nanofabrication by STEM using a focused electron beam. The diameters of the nanostructures grown ranged from 4 to 20 nm depending on the size of the electron beam. Magnetic nanostructures were also obtained using an iron-containing precursor gas, Fe(CO)5. The freestanding iron nanoantennas were examined by electron holography. The magnetic field was observed to leak from the nanostructure body which appeared to act as a 'nanomagnet'. The third example described is the effect of a vacuum on the size and growth process of fabricated nanodots containing W in an ultrahigh-vacuum field-emission TEM (UHV-FE-TEM). The size of the dots can be controlled by changing the dose of electrons and the partial pressure of the precursor. The smallest particle size obtained was about 1.5 nm in diameter, which is the smallest size reported using this method. Finally, the importance of a smaller probe and a higher electron-beam current with atomic resolution is emphasized and an attempt to develop an ultrahigh-vacuum spherical aberration corrected STEM (Cs-corrected STEM) at NIMS is reported.

Fabrication and characterization of nanostructures on insulator substrates by electron-beam-induced deposition.

The fabrication, characterization, and decoration with metallic nanoparticles of nanostructures such as nanowhiskers, nanodendrites, and fractal-like nanotrees on insulator substrates by electron-beam-induced deposition (EBID) are reviewed. Nanostructures with different morphologies of whiskers, dendrites, or trees are fabricated on insulator (Al2O3 or SiO2) substrates by EBID in transmission electron microscopes by controlling the irradiation conditions such as the electron beam intensity. The growth of the nanostructure is related to the accumulation of charges on the surface of a substrate during electron-beam irradiation. A high concentration of the target metallic element and nanocrystal grains of the element are contained in the fabricated nanostructures. The process of growth of the nanostructures is explained qualitatively on the basis of mechanisms in which the formation of the nanostructures is considered to be related to the nanoscaled unevenness of the charge distribution on the surface of the substrate, the movement of the charges to the convex surface of the substrate, and the accumulation of charges at the tip of the grown nanostructure. Novel composite structures of Pt nanoparticle/tungsten (W) nanodendrite or Au nanoparticle/W nanodendrite are fabricated by the decoration of W nanodendrites with metallic elements. Because they have superior features, such as a large specific surface area, a freestanding structure on substrates, a typical size of several nanometers of the tip or the branch, and high purity, the nanostructures may have applications in technologies such as catalysts, sensors, and electron emitters. However, there are still some subjects that should be further studied before their application.

Fabrication and characterization of cellular iron nanocrystalline film.

Cellular iron nanocrystalline film was fabricated on carbon substrate by electron beam chemical vapor deposition (EB-CVD). The film was made up of single alpha-iron cubes with {100} facets ranging from several tens to 200 nm. The thickness and distribution of the film could be controlled by adjusting the irradiation position and duration of the electron beam. The integration of well-faceted nanocrystals enables the film to have a high ratio of free surfaces, which are essential for applications in chemical catalysis and energy absorption. The application of this film as a substrate for further nanofabrication was demonstrated.

Second-harmonic spectroscopy of surface immobilized gold nanospheres above a gold surface supported by self-assembled monolayers.

We have investigated linear and nonlinear optical properties of surface immobilized gold nanospheres (SIGNs) above a gold surface with a gap distance of a few nanometers. The nanogap was supported by amine or merocyanine terminated self-assembled monolayers (SAMs) of alkanethiolates. A large second-harmonic generation (SHG) was observed from the SIGN systems at localized surface plasmon resonance condition. The maximum enhancement factor of SHG intensity was found to be 3 x 10(5) for the SIGN system of nanospheres 100 nm in diameter with a gap distance of 0.8 nm. The corresponding susceptibility was estimated to be chi((2))=750 pmV (1.8 x 10(-6) esu). In the SIGN system supported with the merocyanine terminated SAMs, the SHG response was also resonant to the merocyanine in the nanogap. It was found that the SHG response of the SIGN systems is strongly frequency dependent. This leads us to conclude that the large chi((2)) is caused by enhanced electric fields at the localized surface plasmon resonance condition and is not due to an increase of the surface susceptibility following from the presence of the gold nanospheres. The observed SHG was consistent with the theoretical calculations involving Fresnel correction factors, based on the quasistatic approximation.

Ultrahigh-vacuum third-order spherical aberration (Cs) corrector for a scanning transmission electron microscope.

Initial results from an ultrahigh-vacuum (UHV) third-order spherical aberration (Cs) corrector for a dedicated scanning transmission electron microscopy, installed at the National Institute for Materials Science, Tsukuba, Japan, are presented here. The Cs corrector is of the dual hexapole type. It is UHV compatible and was installed on a UHV column. The Ronchigram obtained showed an extension of the sweet spot area, indicating a successful correction of the third-order spherical aberration Cs. The power spectrum of an image demonstrated that the resolution achieved was 0.1 nm. A first trial of the direct measurement of the fifth-order spherical aberration C5 was also attempted on the basis of a Ronchigram fringe measurement.

TEM sample preparation using a new nanofabrication technique combining electron-beam-induced deposition and low-energy ion milling.

A new TEM sample preparation technique using electron-beam-induced deposition combined with low-energy ion milling was used to fabricate for two different shapes of sample, conical and plate. High-quality HREM images can be obtained from samples prepared by this technique. A desired sample position can be obtained with high accuracy, and the total sample preparation time can be much less than conventional techniques. Because the gas deposition system used can easily be integrated in a conventional SEM, the method can be performed in any laboratory equipped with a SEM and an ion milling machine.

Dynamic Monte Carlo simulation on the electron-beam-induced deposition of carbon, silver, and tungsten supertips.

The process of electron-beam-induced deposition (EBID) was simulated with a dynamic Monte Carlo profile simulator, and the growth of carbon, silver, and tungsten supertips was investigated to study the dependence of material composition on the spatial resolution of EBID. Because light atoms have a smaller scattering angle and a longer mean free path, the carbon supertip has the smallest lateral size and the highest aspect ratio of a bottom tip compared to silver and tungsten supertips. Thus the best spatial resolution of EBID can be achieved on materials of low atomic number. The calculation also indicated a significant contribution of primary electrons to the growth of a supertip in EBID, which is consistent with the experimental observations. These results lead to a more comprehensive understanding of EBID, which is a complex interaction process between electrons and solids.

Growth of tungsten nanodendrites on SiO2 substrate using electron-beam-induced deposition.

Tungsten nanodendrite structures were fabricated on an insulator SiO2 substrate using an electron-beam-induced deposition process in a high voltage transmission electron microscope. The effect of electron beam accelerating voltage on the nanodendrite structures was investigated. The morphologies and their growth rates did not have obvious difference for the deposition at accelerating voltages from 400 to 1000 kV. A mechanism for the growth and morphology of the nanodendrite structure was proposed involving charge-up produced on the surface of the substrate, movement of charges to and accumulation at the convex surface of the substrate and the tips of the deposits. High-energy electron irradiation enhanced diffusion of W atoms in the nanodendrites, promoted crystallization of W grains, so that more crystallized W nanodendrite structures were achieved by the electron-beam-induced deposition process using higher energy electron beams.

Direct UHV-TEM observation of palladium clusters on a silicon surface.

About 1 monolayer of palladium was deposited onto a silicon (111) 7 x 7 surface at a temperature of about 550 K inside an ultrahigh vacuum transmission electron microscope, resulting in formation of Pd2Si nanoislands and a 1 x 1 surface layer. Pd clusters created from an excess of Pd atoms on the 1 x 1 surface layer were directly observed by in situ plan view high-resolution transmission electron microscopy. When an objective aperture was introduced so that electron diffractions less than 0.20 nm were filtered out, the lattice structure of the 1 x 1 surface with 0.33 nm spacing and the Pd clusters with a trimer shape were visualized. It was found that image contrast of the 1 x 1 lattice on the specific height terraces disappeared, and thereby an atomic structure of the Pd clusters was clearly observed. The appearance and disappearance of the 1 x 1 lattice was explained by the effect of the kinematical diffraction. It was identified that a Pd cluster was composed of three Pd atoms without a centered Si atom, which is consistent with the model proposed previously. The feature of the Pd clusters stuck at the surface step was also described.

Detection of iron-oxide layer on the surface of iron nitride using high-resolution electron microscopy and Fourier filtering.

High-resolution electron microscopy (HREM) was used to detect the surface Fe3O4 iron-oxide layer formed on [011] Fe4N iron nitride due to electron irradiation in the transmission electron microscope. The existence of a surface oxide layer was confirmed by both image processing and through-focus observation. Images of the iron oxide were revealed using the process of fast Fourier transformation (FFT) of experimental HREM images, filtering of the FFT patterns and inverse FFT. By through-focus observation, HREM images of iron oxide were obtained based on the tuning of contrast transfer function. Fourier filtering is effective for examining the beginning of phase transformation, because at this stage the diffraction spots of iron oxide are too weak to be detected. At the time when the iron oxide layer has developed to some extent, through-focus observation is useful to obtain an image of oxide layers.

Electron microscopy observation of interface in diffusion-bonded copper joint.

The microstructure at the interface of diffusion-bonded joints of oxygen-free high-conductivity copper for two kinds of surface conditions, with and without argon ion bombardment treatment, was investigated using scanning and high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that argon ion bombardment effectively removed the surface oxide film layer and lowered the height of the surface asperity, so that inclusion formation was decreased and void shrinkage time was shortened at the interface of the bonded copper joints, and the tensile strength of diffusion-bonded copper joints was improved obviously.

Behavior of metal nanoparticles in the electron beam.

Fabrication and structural observation of In, Pd and Mo nanoparticles deposited on Si(110) substrates were performed in an ultrahigh vacuum field emission transmission electron microscope. In situ and/or dynamic observation of In nanoparticles showed fluctuation of their structures. The smaller particles of size of 3-5 nm showed frequent fluctuation, while the nanoparticles of more than 10 nm in size showed relatively slower fluctuation. The bigger nanoparticles showed coalescence with a weaker beam. Pd nanoparticles of size of 3-5 nm showed structural fluctuation after 10-30 s of electron beam irradiation. Stronger beam irradiation resulted in the dissipation of the nanoparticles probably due to diffusion. Mo nanoparticles of size of 3-5 nm never showed structural fluctuation. Intensive electron beam irradiation resulted in the dissipation of the particles. The difference in structural fluctuation depending on the metal and the beam intensity, and the peculiar coalescence of In nanoparticles are discussed qualitatively.

Ordering in a fluid inert gas confined by flat surfaces.

High-resolution transmission electron microscopy images of room-temperature fluid xenon in small faceted cavities in aluminum reveal the presence of three well-defined layers within the fluid at each facet. Such interfacial layering of simple liquids has been theoretically predicted, but observational evidence has been ambiguous. Molecular dynamics simulations indicate that the density variation induced by the layering will cause xenon, confined to an approximately cubic cavity of volume approximately 8 cubic nanometers, to condense into the body-centered cubic phase, differing from the face-centered cubic phase of both bulk solid xenon and solid xenon confined in somewhat larger (>/=20 cubic nanometer) tetradecahedral cavities in face-centered cubic metals. Layering at the liquid-solid interface plays an important role in determining physical properties as diverse as the rheological behavior of two-dimensionally confined liquids and the dynamics of crystal growth.